TW201606597A - Conductive laminated body for touch panel, touch panel, transparent conductive laminated body - Google Patents

Abstract

The invention provides conductive laminated body for touch panel, touch panel and transparent conductive laminated body that containing substrate and pattern shape metal layer. Upon observing from the side of the substrate, the aforesaid pattern shape metal layer may be deemed darker from sight. The conductive laminated body for touch panel is provided with substrate of which have two main surfaces, pattern shape coated layer that installed on at least one main surface of the substrate, which comprises functional groups that can interact with the metal ions and the pattern shape metal layer that set on the pattern shape coated layer. Further, the aforesaid pattern shape coated layer comprises metal components that constituted pattern shape metal layer. Upon using energy dispersive X-ray analysis to analyze the composition of the cross sections of the pattern shape coated layer and the pattern shape metal layer, comparing to the intensity of the average peak of metal component of the pattern shape metal layer, the intensity ratio of the average peak of metal component of the pattern shape coated layer is 0.5~0.95.

Description

Conductive laminated body for touch panel, touch panel, transparent conductive laminated body

The present invention relates to a conductive laminate for a touch panel, a touch panel, and a transparent conductive laminate.

A conductive laminated body in which metal thin wires are formed on a substrate is widely used in electromagnetic wave shielding materials, touch panels, transparent planar heat generating bodies, and the like of various display devices. In particular, in recent years, in the mobile phone, the portable game machine, and the like, the mounting rate of the touch panel has been increasing, and the demand for the conductive laminated body for the capacitive touch panel capable of detecting multiple points has been rapidly increasing.

Further, as a technique for forming a metal layer, a plating method is known. For example, Patent Document 1 discloses a transparent conductive film having a coating film and a patterned metal layer, which is a photosensitive film containing an electroless plating catalyst. The material is formed into a film having a specific pattern by exposure through a photomask, and the pattern metal layer is formed by electroless plating on the film. Further, in the column of the example of Patent Document 1, colloidal palladium (palladium particles) was used as the electroless plating catalyst.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-170421

In recent years, as the visibility of touch panels has been demanded, it has been sought to suppress external light reflection through a metal layer (metal wiring layer) in the touch panel. In order to satisfy such characteristics, the metal layer is required to be regarded as being blacker. Black. In particular, in the case where a mesh (mesh pattern) metal layer made of copper is used as the sensor electrode in the touch panel, this requirement is enhanced. Further, when the touch panel includes a conductive laminated body including a substrate and a patterned metal layer disposed on the substrate, the substrate is often disposed on the viewing side.

The present inventors evaluated the characteristics of the patterned metal layer (patterned copper layer) formed by the plating method using colloidal palladium described in Patent Document 1, and as a result, the color tone of the patterned metal layer was slightly observed from the side of the coating film. There are colors that require further blackening.

In view of the above, an object of the present invention is to provide a conductive laminated body for a touch panel comprising a substrate and a patterned metal layer, and the patterned metal layer is regarded as blacker black when viewed from the substrate side.

Further, another object of the present invention is to provide a touch panel and a transparent conductive laminate including the above-described conductive laminate for a touch panel.

[Means for solving the problem]

The present inventors conducted intensive studies on the problems of the prior art, and as a result, found that a plated layer formed by disposing a composition containing a specific component on a substrate, metal ions are applied to the plated layer, and plating treatment is performed. The formation of a metal layer can solve the above problems.

That is, the inventors have found that the above problems can be solved by the following configuration.

(1) A conductive laminated body for a touch panel, comprising:

a substrate having two main faces;

a patterned plated layer disposed on at least one major surface of the substrate and having a functional group that interacts with the metal ions;

a patterned metal layer disposed on the patterned plated layer;

A metal component constituting the patterned metal layer is included in the patterned plated layer;

When the cross-section of the pattern-coated layer and the patterned metal layer is analyzed by energy dispersive X-ray analysis, the pattern-like layer is applied to the average peak intensity of the metal component constituting the pattern-shaped metal layer. The ratio of the average peak intensity of the metal component source contained is 0.5 to 0.95.

(2) The conductive laminated body for a touch panel according to the above aspect, wherein a patterned plated layer and a patterned metal layer are disposed on each of the two main surfaces of the substrate.

(3) A conductive laminated body for a touch panel, which has a substrate, a pattern-like resin layer, and a patterned metal layer in the order described, the substrate having two main faces, and the patterned resin layer is disposed on at least one main body of the substrate On the surface, the patterned metal layer is disposed on the patterned resin layer; wherein the conductive laminated body for the touch panel satisfies at least one of the following requirements A and B.

Requirement A: Metal particles having an average particle diameter of 10 to 1000 nm exist in a surface layer region of 500 nm in the direction of the pattern-like resin layer from the interface between the pattern-like resin layer and the pattern-like metal layer.

Requirement B: The interface between the pattern-like resin layer and the patterned metal layer has an uneven shape, and the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 to 1000 nm.

The conductive laminate for a touch panel according to any one of the aspects of the present invention, wherein the substrate is a glass substrate or a resin substrate.

(5) The conductive laminated body for a touch panel according to any one of (1) to (4), wherein an undercoat layer is disposed adjacent to a main surface of the substrate.

The conductive laminate for a touch panel according to any one of the above aspects, wherein the patterned metal layer contains copper.

(7) A conductive laminated body for a touch panel according to any one of (1) to (6).

(8) A transparent conductive laminated body having:

a substrate having two main faces;

a patterned plated layer disposed on at least one major surface of the substrate and having a functional group that interacts with the metal ions;

a patterned metal layer disposed on the patterned plated layer;

A metal component constituting the patterned metal layer is included in the patterned plated layer;

When the cross-section of the pattern-coated layer and the patterned metal layer is analyzed by energy dispersive X-ray analysis, the pattern-like layer is applied to the average peak intensity of the metal component constituting the pattern-shaped metal layer. The ratio of the average peak intensity of the metal component source contained is 0.50 to 0.95.

[Effects of the Invention]

According to the present invention, it is possible to provide a conductive laminated body for a touch panel including a substrate and a patterned metal layer, and the patterned metal layer is regarded as blacker black when viewed from the substrate side (in other words, the touch panel) The back surface (the surface on the substrate side) of the patterned metal layer of the conductive laminate is regarded as blacker black.

Moreover, the present invention can also provide a touch panel and a transparent conductive laminated body including the above-described conductive laminated body for a touch panel.

Hereinafter, the conductive laminated body for a touch panel of the present invention will be described in detail. In addition, the numerical range represented by "-" in this specification is the range which contains the numerical value of the [ before-

First, one of the features of the conductive laminate for a touch panel of the present invention (particularly, the first embodiment and the second embodiment described later) and the prior art are characterized in that a pattern is formed. After the plating layer, when the patterned metal layer is formed by the plating treatment, a catalyst-imparting liquid containing a plating catalyst exhibiting a specific pH or a precursor thereof is used.

In one embodiment of the conductive laminated body for a touch panel, as described below, the patterned metal layer is formed by applying a metal ion to the plating layer of the pattern formed of the composition containing the specific component and performing a plating treatment. . In the case where the pattern-like metal layer is formed by such a method, first, a treatment for imparting a metal ion functioning as a plating catalyst to the pattern-formed layer to be plated is performed before the plating treatment is performed. At this time, the inventors have recognized that although a catalyst-imparting liquid containing a metal ion is used, the behavior of the subsequent plating treatment greatly differs depending on the pH thereof. In other words, when a catalyst-imparting liquid exhibiting a specific pH is used, in a subsequent plating treatment, a metal layer is formed at a specific position on the pattern-shaped plated layer to form a patterned metal layer. When such a patterned metal layer is observed from the back side (the side of the pattern-formed layer), it is considered to be black as compared with the aspect of Patent Document 1, and a desired effect is obtained. The reason why such a desired effect is obtained is that a metal component constituting the patterned metal layer is included in the pattern-coated layer. More specifically, when the above-described catalyst-imparting liquid is used, the amount of metal ions imparted in the pattern-formed layer is increased, and a desired pattern-like metal layer is easily formed by the subsequent plating treatment. At this time, although the detailed reason is not clear, the inventors have recognized that precipitation of a metal component constituting the patterned metal layer is also affected in the pattern-like plated layer, which affects the visibility of the patterned metal layer.

On the other hand, when a liquid is applied to a catalyst whose pH is not a specific range, there may be a problem that a pattern-like metal layer is not obtained at all, or a portion other than the pattern-formed layer is also subjected to metal chromatography. Applications in touch panel applications are limited.

Further, as another reason for obtaining the effects of the present invention, the following aspects are considered.

As described above, in the case where the metal is analyzed to the patterned plated layer, the catalyst metal or the plated metal on the surface of the plated layer is complicatedly entered into the plated layer, and the patterned metal is formed. The layer and the interface of the pattern-coated layer form a fine concavo-convex shape. At this time, the metal that has entered the layer to be plated exists in the form of independent metal particles inside the plated layer, and also adheres to the surface of the patterned metal layer in the patterned metal layer and the plated layer. The case where an irregular shape having irregularities is formed at the interface. When such a conductive laminated body for a touch panel is viewed from the substrate side, light is absorbed by the presence of the metal particles or light reflection is suppressed by the fine uneven structure on the side of the plated layer of the patterned metal layer. Therefore, as a result, the back side of the patterned metal layer is regarded as blacker black. Further, in the pattern-like metal layer formed by the plating treatment, the metals are densely packed between each other, and thus the conductive properties are also excellent.

In addition, in the case of using the above-described plating treatment, the process temperature at the time of production can be kept at a low temperature (for example, 100 ° C or lower), and it is not necessary to perform high-temperature heat treatment performed in sputtering or the like, and damage to the substrate can be suppressed.

Furthermore, in the above-mentioned Patent Document 1, since the photosensitive electroless plating catalyst is contained in the photosensitive material, when the exposure is performed in order to pattern the photosensitive material, the particulate electroless plating catalyst is generated. Scattering does not negate the resulting patterned line width. On the other hand, in the method of the present invention, first, patterning of the layer to be plated is performed, and then metal ions are applied, so that a pattern having a finer line width can be formed, and as a result, it can be plated in the thin pattern. A patterned metal layer having a thin line width is formed on the layer.

In the following description, the patterned metal layer is considered to be black as described above, and the back side of the patterned metal layer (the side of the patterned plated layer) is considered to be black.

<<First embodiment>>

Fig. 1 is a cross-sectional view showing a first embodiment of a conductive laminated body for a touch panel of the present invention.

A conductive laminated body for a touch panel (hereinafter also referred to simply as "layered body") 100 includes a substrate 12, a patterned plated layer 20, and a patterned metal layer 22.

First, the manufacturing method of the laminated body will be described in detail first, and then the configuration of the laminated body will be described in detail.

<Method of Manufacturing Laminates>

The method for producing the laminated body includes a step of forming a patterned plated layer on the substrate (Step 1) and a step of forming a patterned metal layer on the patterned plated layer (Step 2).

The components, materials, and processes used in each step will be described in detail below.

[Step 1: Pattern-formed layer-forming layer forming step]

Step 1 is a step of patterning a composition for forming a layer to be plated containing a compound having a functional group (hereinafter also referred to as "interactive group") which interacts with a metal ion and a polymerizable group. Energy is applied to form a patterned plated layer on the substrate. More specifically, the process is as follows: First, as shown in FIG. 2(A), a coating film 30 for forming a composition for forming a plating layer is formed on a substrate 12, as shown in FIG. 2(B). The coating film 30 is energized in a pattern as indicated by a black arrow to promote the reaction of the polymerizable group and to be cured, and then remove the region where no energy is applied, thereby obtaining a patterned plated layer 20 (Fig. 2(C)). .

In the pattern-formed layer to be formed formed in the above-described step, metal ions are adsorbed (adhered) in the step 2 to be described later according to the function of the interactive group. That is, the pattern-shaped plated layer functions as a good receiving layer of metal ions. In addition, the polymerizable group is used for the bonding between the compounds by the curing treatment by energy application, and a patterned coating layer having excellent hardness and hardness (hardness and hardness) can be obtained.

First, the components and materials used in this step will be described in detail below, and the process of the process will be described in detail later.

(substrate)

The substrate is not particularly limited as long as it has two main faces and supports a patterned plated layer to be described later. As the substrate, an insulating substrate is preferable, and more specifically, a resin substrate, a ceramic substrate, a glass substrate, a liquid crystal cell glass substrate, or the like can be used.

Examples of the material of the resin substrate include polyethylene terephthalate, polyethylene naphthalate, polyether oxime, polyacrylic resin, urethane resin, polyester, polycarbonate, and poly. Anthracene, polyamine, polyarylate, polyolefin, cellulose resin, polyvinyl chloride, cycloolefin resin, and the like. Among them, polyethylene terephthalate, polyethylene naphthalate or polyolefin is preferred.

The thickness (mm) of the substrate is not particularly limited, and is preferably 0.05 to 2 mm, and more preferably 0.1 to 1 mm from the viewpoint of balance between handleability and thickness reduction.

Further, the substrate preferably transmits light appropriately. Specifically, the total light transmittance of the substrate is preferably 85 to 100%.

Further, the substrate may have a multilayer structure, for example, as one layer thereof, may contain a functional film. In addition, the substrate itself may be a functional film. Although not particularly limited, examples of the functional film include a polarizing plate, a retardation film, a cover plastic, a hard coat film, a barrier film, an adhesive film, an electromagnetic wave mask film, a heat radiation film, an antenna film, and a touch. A wiring film for devices other than the panel.

In particular, as a polarizing plate, for example, an NPF series (manufactured by Nitto Denko Corporation) or an HLC2 series (manufactured by Sanritz Co., Ltd.) can be used as the polarizing plate, and a retardation film can be used. WV film (manufactured by Fujifilm Co., Ltd.), etc., can be used as a cover plastic, such as FAlNDE (manufactured by Dainippon Printing Co., Ltd.), Technolloy (manufactured by Sumitomo Chemical Co., Ltd.), Iupilon (manufactured by Mitsubishi Gas Chemical Co., Ltd.), Silplus (manufactured by Nippon Steel & Sumitomo Metal Co., Ltd.), ORGA (Japan) For the hard coat film, H series (manufactured by Lintec Co., Ltd.), FHC series (manufactured by Higashiyama Film Co., Ltd.), KB film (manufactured by KIMOTO Co., Ltd.), or the like can be used as the hard coat film. They form the coated layer of the present invention on the surface of each functional film.

In the polarizing plate or the retardation film, cellulose triacetate can be used as described in JP-A-2007-26426. However, from the viewpoint of resistance to the plating process, cellulose triacetate may be changed to The cycloolefin (co)polymer is used, and examples thereof include ZEONOR (manufactured by Zeon, Japan).

(Composition for forming a layer to be plated)

The composition for forming a layer to be plated contains a compound having a functional group and a polymerizable group which interact with a metal ion.

The functional group that interacts with the metal ion means a functional group that can interact with the metal ion to be applied to the patterned plated layer in the later-described step, and for example, a functional group capable of forming electrostatic interaction with the metal ion can be used or can be used. The metal ion forms a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, and the like of the ligand.

Specific examples of the interactive group include an amino group, a decylamino group, a guanidino group, a ureido group, a tertiary amino group, an ammonium group, a decyl group, a triazine ring, a triazole ring, and a benzotriene group. Azyl, imidazolyl, benzimidazolyl, quinolyl, pyridyl, pyrimidinyl, pyrazinyl, oxazolinyl, quinoxalinyl, fluorenyl, triazinyl, acridinyl, pyridazinyl, pyrrole Alkyl, pyrazolyl, anilino, a group containing an alkylamine structure, a group containing an isocyanuric structure, a nitro group, a nitroso group, an azo group, a diazo group, an azide group, a cyano group, a nitrogen-containing functional group such as a cyanate group (RO-CN); an ether group, a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, a carbonate group, a carbonyl group, an ester group, a group having an N-oxide structure, and an S-oxide-containing structure. An oxygen-containing functional group such as a group or a group containing an N-hydroxy structure; a thienyl group, a thiol group, a thiourea group, a thiocyanuric acid group, a benzothiazolyl group, a decyltriazinyl group, a thioether group, a thiol group, Amidino group, sulfhydryl group, sulfite group, group containing a ruthenium imine structure, a group containing a sulphur oxide salt structure, a sulfonic acid group, a sulfonate-containing ester a sulfur-containing functional group such as a group; a phosphorus-containing functional group such as a phosphate group, a phosphonium amino group, a phosphino group, or a phosphate group-containing group; a group containing a halogen atom such as chlorine or bromine, etc., and a functional group capable of adopting a salt structure Among them, it is also possible to use their salts.

Among them, a polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group or a boronic acid group, an ether group or a cyano group is particularly preferable because of high polarity and high adsorption ability with metal ions, and the like, and a carboxyl group or a cyano group is more preferable.

In the compound, the interactive group may contain two or more kinds. Further, the number of the interactive groups contained in the compound is not particularly limited, and may be one or two or more.

The polymerizable group is a functional group capable of forming a chemical bond by energy supply, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among them, a radical polymerizable group is preferred from the viewpoint of further excellent reactivity. Examples of the radical polymerizable group include an acrylate group (acryloxy group), a methacrylate group (methacryloxy group), an itaconate group, a butenoate group, and a methacrylic acid. An unsaturated carboxylate group such as an ester group or a maleate group; a styryl group, a vinyl group, a acrylamide group, a methacrylamide group or the like. Among them, a methacryloxy group, a propylene methoxy group, a vinyl group, a styryl group, an acrylamide group, a methacrylamide group, and a methacryloxy group, an acryloxy group, a styryl group are particularly preferable. .

In the compound, the polymerizable group may contain two or more kinds. Further, the number of the polymerizable groups contained in the compound is not particularly limited, and may be one or two or more.

The above compound may be a low molecular compound or a high molecular compound. The low molecular compound means a compound having a molecular weight of less than 1,000, and the polymer compound means a compound having a molecular weight of 1,000 or more.

It should be noted that the low molecular compound having the above polymerizable group corresponds to a so-called monomer. Further, the polymer compound may be a polymer having a specific repeating unit.

Further, as the compound, one type may be used alone or two or more types may be used in combination.

When the compound is a polymer, the weight average molecular weight of the polymer is not particularly limited, and from the viewpoint of more excellent handleability such as solubility, it is preferably 1,000 or more and 700,000 or less, and more preferably 2,000 or more and 200,000 or less. From the viewpoint of polymerization sensitivity, it is particularly preferably 20,000 or more.

The synthesis method of the polymer having such a polymerizable group and an interactive group is not particularly limited, and a known synthesis method can be used (see Japanese Patent Laid-Open Publication No. 2009-280905 [0097] to [0125].

(Appropriate way of polymer 1)

The first preferred embodiment of the polymer includes a repeating unit having a polymerizable group represented by the following formula (a) (hereinafter referred to as a polymerizable group unit for convenience) and the following formula (b) a copolymer of a repeating unit of an interactive group (hereinafter also referred to as an interactive group unit for convenience).

[Chemical 1]

In the above formula (a) and formula (b), R ¹ to R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group (e.g., a methyl group, an ethyl group, a propyl group, a butyl group or the like). Further, the type of the substituent is not particularly limited, and examples thereof include a methoxy group, a chlorine atom, a bromine atom, and a fluorine atom.

Note that, as R ^1, preferably a hydrogen atom, a methyl group substituted with a bromine atom or a methyl group. As R ² , a hydrogen atom, a methyl group or a methyl group substituted with a bromine atom is preferred. As R ³ , a hydrogen atom is preferred. As R ⁴ , a hydrogen atom is preferred. R ⁵ is preferably a hydrogen atom, a methyl group or a methyl group substituted by a bromine atom.

In the above formula (a) and formula (b), X, Y and Z each independently represent a single bond, or a substituted or unsubstituted binary organic group. The dibasic organic group may, for example, be a substituted or unsubstituted dibasic aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, such as an alkylene group such as a methylene group, an ethylene group or a propenyl group), a substitution or no Substituted dibasic aromatic hydrocarbon groups (preferably having 6 to 12 carbon atoms, such as phenylene), -O-, -S-, -SO ₂ -, -N(R)-(R:alkyl), - CO-, -NH-, -COO-, -CONH- or a group obtained by combining them (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.), etc.

X, Y and Z are preferably a single bond, an ester group (-COO-) or a guanamine group (-CONH-), from the viewpoint that the synthesis of the polymer is easy and the adhesion of the patterned metal layer is more excellent. The ether group (-O-) or the substituted or unsubstituted divalent aromatic hydrocarbon group is more preferably a single bond, an ester group (-COO-) or a decylamino group (-CONH-).

In the above formula (a) and the formula (b), L ¹ and L ² each independently represent a single bond, or a substituted or unsubstituted dibasic organic group. The definition of the binary organic group has the same meaning as the above-described binary organic group in X, Y and Z.

L ¹ is preferably an aliphatic hydrocarbon group or a binary organic group having a urethane bond or a urea bond (for example, an aliphatic group) from the viewpoint that the synthesis of the polymer is easy and the adhesion of the patterned metal layer is more excellent. Hydrocarbyl), wherein a group having a total number of carbon atoms of 1 to 9 is preferred. Note that here, L is the total number ^of carbon atoms refers to the total number of carbon is a substituted or unsubstituted dibasic organic group represented by L ¹ contained in the atoms.

In addition, L ² is preferably a single bond or a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof, from the viewpoint of further excellent adhesion of the patterned metal layer. Among them, L ² is preferably a single bond or a total number of carbon atoms of from 1 to 15, and particularly preferably unsubstituted. Note that here, L ² is the total number of carbon atoms refers to the total number of carbon is a substituted or unsubstituted dibasic organic group represented by L ² contained in the atoms.

In the above formula (b), W represents an interactive group. The definition of an interactive group is as described above.

The content of the polymerizable group unit is preferably 5 to 50% by mole based on the reactivity (curability, polymerizability) and the gelation at the time of the synthesis, and is more preferably 5 to 50% by mole based on the total of the repeating units in the polymer. 5 to 40% by mole.

Further, the content of the above-mentioned interactive group unit is preferably 5 to 95% by mole, and more preferably 10 to 95% by mole based on the total repeating unit in the polymer from the viewpoint of the adsorption property to the metal ion.

(A suitable way for the polymer 2)

The second preferred embodiment of the polymer includes a copolymer containing a repeating unit represented by the following formula (A), formula (B), and formula (C).

[Chemical 2]

The repeating unit represented by the formula (A) is the same as the repeating unit represented by the above formula (a), and the description of each group is also the same.

(B) repeating units represented by R ^5, X, and L ² represented by the above formula (b) and repeating units R ^5, X and L are the same as the formula ^2, each of the groups described is also the same.

Wa in the formula (B) represents a group which interacts with a metal ion other than the hydrophilic group represented by V described later or a precursor group thereof. Among them, a cyano group and an ether group are preferred.

In the formula (C), R ⁶ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group.

In the formula (C), U represents a single bond, or a substituted or unsubstituted binary organic group. The definition of the binary organic group has the same meaning as the above-mentioned binary organic group represented by X, Y and Z. U is preferably a single bond, an ester group (-COO-), a guanamine group (-CONH-), or an ether group from the viewpoint that the synthesis of the polymer is easy and the adhesion of the patterned metal layer is more excellent. O-), or a substituted or unsubstituted dibasic aromatic hydrocarbon group.

In the formula (C), L ³ represents a single bond, or a substituted or unsubstituted binary organic group. The definition of the binary organic group is the same as the meaning of the binary organic group represented by the above L ¹ and L ² . As L ^3, from a synthetic polymer easy adhesion aspects patterned metal layer is more excellent in consideration of, preferably a single bond aliphatic hydrocarbon group or dibasic, dibasic aromatic hydrocarbon group or a group formed by a combination thereof .

In the formula (C), V represents a hydrophilic group or a precursor group thereof. The hydrophilic group is not particularly limited as long as it exhibits hydrophilicity, and examples thereof include a hydroxyl group and a carboxylic acid group. Further, the precursor group of the hydrophilic group means a group which can form a hydrophilic group by a specific treatment (for example, treatment with an acid or hydrazine), and examples thereof include THP (2-tetrahydropyranyl group). Protected carboxyl groups and the like.

As the hydrophilic group, an ionic polar group is preferred from the viewpoint of interaction with metal ions. Specific examples of the ionic polar group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group. Among them, a carboxylic acid group is preferred from the viewpoint of moderate acidity (no decomposition of other functional groups).

The preferred content of each unit in the second preferred embodiment of the above polymer is as follows.

The content of the repeating unit represented by the formula (A) is preferably 5 to 50% by mole based on the reactivity (curability, polymerizability) and the gelation at the time of inhibiting synthesis, with respect to all the repeating units in the polymer. More preferably, it is 5 to 30 mol%.

The content of the repeating unit represented by the formula (B) is preferably from 5 to 75 mol%, more preferably from 10 to 70 mol%, based on the total of the repeating units in the polymer.

The content of the repeating unit represented by the formula (C) is preferably from 10 to 70 mol%, more preferably from 20 to 60, based on the developability of the aqueous solution and the wet adhesion resistance, with respect to all the repeating units in the polymer. The mole % is more preferably 30 to 50% by mole.

Specific examples of the polymer include a polymer described in paragraphs [0106] to [0112] of JP-A-2009-007540, and paragraphs [0065] to [0070] of JP-A-2006-135271. The polymer described in the above, the polymer described in paragraphs [0030] to [0108] of US2010-080964.

The polymer can be produced by a known method (for example, the method in the literature cited above).

(appropriate way of monomer)

When the above compound is a so-called monomer, one of the suitable embodiments may be a compound represented by the formula (X).

[Chemical 3]

In the formula (X), R ¹¹ to R ¹³ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. The unsubstituted alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. Further, examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group substituted with a methoxy group, a chlorine atom, a bromine atom or a fluorine atom. Further, as R ¹¹ , a hydrogen atom or a methyl group is preferred. As R ¹² , a hydrogen atom is preferred. As R ¹³ , a hydrogen atom is preferred.

L ¹⁰ represents a single bond or a binary organic group. The divalent organic group may, for example, be a substituted or unsubstituted aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a substituted or unsubstituted aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), and -O. -, -S-, -SO ₂ -, -N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH- or a group combining them (for example An alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, etc.).

The substituted or unsubstituted aliphatic hydrocarbon group is preferably a group obtained by substituting a methylene group, an ethylene group, a propylene group or a butylene group or a group thereof with a methoxy group, a chlorine atom, a bromine atom or a fluorine atom.

The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenylene group or a phenylene group substituted with a methoxy group, a chlorine atom, a bromine atom or a fluorine atom.

In the formula (X), as one of suitable methods of L ¹⁰ , a -NH-aliphatic hydrocarbon group or a -CO-aliphatic hydrocarbon group- may be mentioned.

The definition of W is the same as the definition of W in the formula (b), and represents an interactive group. The definition of an interactive group is as described above.

In the formula (X), as a suitable form of W, an ionic polar group is mentioned, and a carboxylic acid group is more preferable.

When the above compound is a so-called monomer, one of other suitable embodiments may be a compound represented by the formula (1).

[Chemical 4]

In the formula (1), R ¹⁰ represents a hydrogen atom, a metal cation or a quaternary ammonium cation. Examples of the metal cation include an alkali metal cation (sodium ion, calcium ion), copper ion, palladium ion, silver ion, and the like. Further, as the metal cation, a monovalent or divalent metal cation is mainly used, and when a divalent metal cation (for example, palladium ion) is used, n which will be described later represents 2.

Examples of the quaternary ammonium cation include a tetramethylammonium ion and a tetrabutylammonium ion.

Among them, a hydrogen atom is preferred from the viewpoint of adhesion of metal ions and metal residue after patterning.

The same meaning as defined in the formula in the definition of L ¹⁰ L ¹⁰ (1) in the above-mentioned formula (X), represents a single bond or dibasic organic group. The definition of a binary organic group is as described above.

It is defined the same as defined in the formula R (1) is ¹¹ ~ R ¹³ of the above-described formula (X) R ¹¹ ~ R ¹³ meaning, represents a hydrogen atom, or a substituted or unsubstituted alkyl. Further, a suitable mode of R ¹¹ to R ¹³ is as described above.

n represents an integer of 1 or 2. Among them, n is preferably 1 from the viewpoint of availability of the compound.

A suitable form of the compound represented by the formula (1) is a compound represented by the formula (2).

[Chemical 5]

In the formula (2), R ¹⁰ , R ¹¹ and n are the same as defined above.

L ¹¹ represents an ester group (-COO-), a guanamine group (-CONH-) or a phenylene group. However, when L ¹¹ is a guanamine group, the polymerizability and solvent resistance (for example, solvent resistance) of the obtained plated layer are improved.

L ¹² represents a single bond or a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, more preferably 3 to 5 carbon atoms) or a divalent aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic. Further, in the case where L ¹² is a single bond, L ¹¹ represents a phenylene group.

The molecular weight of the compound represented by the formula (1) is not particularly limited, and the molecular weight is preferably from 100 to 1,000, and more preferably from 100 to 300, from the viewpoints of volatility, solubility in a solvent, film formability, and handleability.

The content of the above compound in the composition for forming a layer to be plated is not particularly limited, and is preferably 2 to 50% by mass, and more preferably 5 to 30% by mass based on the total amount of the composition. When the content of the above compound is within the above range, the handleability of the composition is excellent, and the control of the layer thickness of the patterned plated layer is easily performed.

From the viewpoint of handleability, it is preferred to include a solvent in the composition for forming a layer to be plated.

The solvent which can be used is not particularly limited, and examples thereof include water; alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, 1-methoxy-2-propanol, glycerin, and propylene glycol monomethyl ether; and acids such as acetic acid. a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; a guanamine solvent such as formamide, dimethylacetamide or N-methylpyrrolidone; a nitrile solvent such as acetonitrile or propionitrile; An ester solvent such as an ester or an ethyl acetate; a carbonate solvent such as dimethyl carbonate or diethyl carbonate; an ether solvent, a glycol solvent, an amine solvent, a thiol solvent, or a halogen solvent.

Among them, an alcohol solvent, a guanamine solvent, a ketone solvent, a nitrile solvent, and a carbonate solvent are preferable.

The content of the solvent in the composition for forming a layer to be plated is not particularly limited, and is preferably from 50 to 98% by mass, and more preferably from 70 to 95% by mass based on the total amount of the composition. When the content of the solvent is within the above range, the handleability of the composition is excellent, and the control of the layer thickness of the pattern-coated layer is easily performed.

A polymerization initiator may be contained in the composition for forming a layer to be plated. By containing a polymerization initiator, the bond between the compounds and the compound and the substrate is further formed, and as a result, a patterned metal layer having more excellent adhesion can be obtained.

The polymerization initiator to be used is not particularly limited, and for example, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. Examples of the photopolymerization initiator include benzophenones, acetophenones, α-aminoalkylphenones, benzoin, ketones, thioxanthones, benzophenes, and benzene. Olequinones, oxime esters, anthrones, tetramethylthiuram monosulfides, bis-indenylphosphine oxides, fluorenylphosphine oxides, anthraquinones, azo compounds, and derivatives thereof .

Moreover, examples of the thermal polymerization initiator include a diazo compound or a peroxide compound.

When the polymerization initiator is contained in the composition for forming a layer to be plated, the content of the polymerization initiator is preferably 0.01 to 1% by mass, and more preferably 0.1 to 0.5% by mass based on the total amount of the composition. When the content of the polymerization initiator is within the above range, the handleability of the composition is excellent, and the adhesion of the obtained patterned metal layer is further improved.

A monomer (which does not include the compound represented by the above formula (X) or formula (1)) may be contained in the composition for forming a layer to be plated. By containing a monomer, the crosslinking density and the like in the plated layer can be appropriately controlled.

The monomer to be used is not particularly limited, and examples of the compound having an addition polymerizable property include a compound having an ethylenically unsaturated bond, and examples of the compound having a ring-opening polymerizable property include a compound having an epoxy group. . Among them, a polyfunctional monomer is preferably used from the viewpoint of improving the crosslinking density in the patterned coating layer and further improving the adhesion of the patterned metal layer. The polyfunctional monomer means a monomer having two or more polymerizable groups. Specifically, a monomer having 2 to 6 polymerizable groups is preferably used.

The molecular weight of the polyfunctional monomer to be used is preferably from 150 to 1,000, and more preferably from 200 to 700, from the viewpoint of molecular mobility in the crosslinking reaction which affects reactivity. In addition, when there are a plurality of polymerizable groups, the interval (distance) between the polymerizable groups is preferably from 1 to 15, more preferably from 6 to 10, in terms of the number of atoms.

Other additives (for example, sensitizer, curing agent, polymerization inhibitor, antioxidant, antistatic agent, ultraviolet absorber, filler, particles, flame retardant, surface active) may be added to the composition for forming a layer to be plated. Agents, lubricants, plasticizers, etc.).

Further, in the above, the composition for forming a layer to be plated containing a compound having an interactive group and a polymerizable group has been described, but it is not limited thereto, and for example, it may contain an interaction property. A composition for forming a layer of a compound of a group and a compound having a polymerizable group.

The definition of the interactive group and the polymerizable group is as described above.

A compound having an interactive group means a compound having an interactive group. The definition of an interactive group is as described above. Such a compound may be a low molecular compound or a polymer compound. A suitable form of the compound having an interactive group is a polymer (for example, polyacrylic acid) having a repeating unit represented by the above formula (b). It should be noted that the polymerizable group is not contained in the compound having an interactive group.

The compound having a polymerizable group is a so-called monomer, and a polyfunctional monomer having two or more polymerizable groups is preferred from the viewpoint that the hardness of the layer to be plated formed is more excellent. As the polyfunctional monomer, specifically, a monomer having 2 to 6 polymerizable groups is preferably used. The molecular weight of the polyfunctional monomer to be used is preferably from 150 to 1,000, and more preferably from 200 to 700, from the viewpoint of molecular mobility in the crosslinking reaction which affects reactivity. In the case where a plurality of polymerizable groups are present, the interval (distance) between the polymerizable groups is preferably from 1 to 15 and more preferably from 6 to 10 in terms of the number of atoms.

(process of process 1)

In the step 1, the composition for forming a layer to be plated is first placed on the substrate, and the method is not particularly limited. For example, the composition for forming a layer to be plated is brought into contact with the substrate to form a layer to be plated. A method of coating a coating (coating layer precursor layer) of the composition. As such a method, for example, a method (coating method) of applying the composition for forming a layer to be plated onto a substrate is exemplified.

In the case of the coating method, the method of applying the composition for forming a layer to be plated on the substrate is not particularly limited, and a known method (for example, spin coating, die coating, dip coating, or the like) can be used.

From the viewpoint of handleability and production efficiency, a composition for forming a layer to be plated is applied onto a substrate, and if necessary, a solvent is removed by drying to form a coating film.

Further, the conditions of the drying treatment are not particularly limited, and from the viewpoint of further excellent productivity, it is preferably carried out at room temperature to 220 ° C (preferably 50 to 120 ° C) for 1 to 30 minutes (preferably 1 to 10 minutes).

The method of imparting energy to the coating film containing the above compound on the substrate in a pattern is not particularly limited. For example, heat treatment, exposure treatment (light irradiation treatment), or the like is preferably used, and from the viewpoint of ending the treatment in a short time, exposure treatment is preferred. By imparting energy to the coating film, the polymerizable group in the compound is activated, and crosslinking occurs between the compounds to cure the layer.

The exposure process uses a UV lamp, light irradiation based on visible light rays, or the like. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. As the radiation, there are electron rays, X rays, ion beams, far infrared rays, and the like. As a specific aspect, a high-illumination scintillation exposure such as a scanning exposure by an infrared laser device, a xenon discharge lamp, or the like, and an infrared lamp exposure can be suitably used.

The exposure time varies depending on the reactivity of the compound and the light source, and is usually from 10 seconds to 5 hours. The exposure energy may be about 10 to 8000 mJ, and preferably 50 to 3000 mJ.

Further, the method of performing the above-described exposure treatment in a pattern is not particularly limited, and a known method can be employed. For example, the coating film can be exposed to light through a mask.

Further, when heat treatment is used as the energy supply, a blast dryer, an oven, an infrared dryer, a heating drum, or the like can be used.

Next, the portion of the coating film where the energy is not applied is removed, and a patterned plated layer is formed.

The above removal method is not particularly limited, and an optimum method is appropriately selected depending on the compound to be used. For example, a method of using an alkaline solution (preferably pH: 13.0 to 13.8) as a developing solution can be mentioned. In the case where the energy-imparting region is removed by using an alkaline solution, a method of immersing a substrate having a coating film to which energy is applied in a solution, a method of applying a developing solution on the substrate, and the like, and preferably immersing may be mentioned. method. In the case of the immersion method, the immersion time is preferably from about 1 minute to 30 minutes from the viewpoints of productivity, workability, and the like.

Further, as another method, a method in which a solvent which dissolves the above compound is used as a developing solution and is immersed therein may be mentioned.

(patterned coated layer)

The thickness of the patterned plated layer formed by the above treatment is not particularly limited, and is preferably 0.01 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.3 to 1.0 μm from the viewpoint of productivity.

The pattern shape of the pattern-formed layer to be plated is not particularly limited, and may be adjusted in accordance with the position at which the pattern-like metal layer to be described later is to be formed, and examples thereof include a mesh pattern and the like. In the case of the mesh pattern, the length W of one side of the lattice (opening) in the mesh pattern is preferably 800 μm or less, more preferably 600 μm or less, or preferably 50 μm or more, and more preferably 400 μm. Further, the shape of the lattice is not particularly limited, and may be a substantially rhombic shape or a polygonal shape (for example, a triangle, a quadrangle, or a hexagon). Further, the shape of one side may be a straight shape, or may be a curved shape or an arc shape.

In addition, the line width of the pattern-formed layer to be plated is not particularly limited, and is preferably 30 μm or less, more preferably 15 μm, more preferably from the viewpoint of low resistance of the pattern-like metal layer disposed on the pattern-formed layer. It is 10 μm, particularly preferably 9 μm or less, and most preferably 7 μm or less, preferably 0.5 μm or more, and more preferably 1.0 μm or more.

[Step 2: Pattern Metal Layer Forming Process]

Step 2 is a step of applying a metal ion to the pattern-formed layer to be formed in the step 1 and plating the pattern-coated layer to which the metal ions are applied, on the pattern-coated layer. A patterned metal layer is formed. As shown in FIG. 2(D), by performing this step, the patterned metal layer 22 is placed on the patterned plated layer 20.

In the following, the step of adding a metal ion to the pattern-formed layer (step 2-1) and the step of performing a plating treatment on the pattern-formed layer to which the metal ion is applied (step 2-2) will be described.

(Step 2-1: Metal Ion Providing Step)

In this step, first, metal ions are applied to the patterned plated layer. The interactive group derived from the above compound adheres (adsorbs) the metal ion to be imparted according to its function. More specifically, metal ions are imparted to the surface to be plated and to the surface of the layer to be plated.

The metal ion can be converted into a plating catalyst by a chemical reaction, and more specifically, a zero-valent metal which is a plating catalyst by a reduction reaction. In this step, after the metal ions are applied to the patterned plated layer, they may be converted into a zero-valent metal by another reduction reaction before being immersed in a plating bath (for example, an electroless plating bath) as a plating catalyst. Alternatively, it may be immersed in a plating bath in the state of metal ions, and changed into a metal (plating catalyst) by a reducing agent in the plating bath.

The metal ion is preferably imparted to the patterned plated layer using a metal salt. The metal salt to be used is not particularly limited as long as it can be dissolved in a suitable solvent and dissociated into a metal ion and a sulfhydryl group (anion), and examples thereof include M(NO ₃ ) _n , MCl _n , and M _2/n (SO). ₄ ), M _3/n (PO ₄ ) (M represents an n-valent metal atom), and the like. As the metal ion, a metal ion obtained by dissociation of the above metal salt can be suitably used. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, ions capable of multidentate coordination, number of functional groups capable of coordination, and catalysts are preferable. From the viewpoint of the ability, Ag ions and Pd ions are particularly preferable. Among them, Pd ions are particularly preferable from the viewpoint of electrical reliability.

As a method of imparting a metal ion to the pattern-formed layer, a method of bringing a metal ion-containing catalyst-imparting liquid into contact with the pattern-formed layer is mentioned. Further, as a method of performing the contact, for example, a catalyst application liquid may be applied onto the pattern-coated layer or a substrate on which the pattern-coated layer is formed may be immersed in the catalyst application liquid.

The pH of the catalyst-imparting liquid is 3.0 to 7.0, and the patterned metal layer is considered to be blacker black (more specifically, when the pattern-shaped metal layer is observed from the side of the pattern-formed layer, the pattern is The pH is preferably from 3.2 to 6.8, and more preferably from 3.5 to 6.6, from the viewpoint that the back side of the metal layer (the side of the patterned layer to be plated) is considered to be blacker black.

When the pH of the catalyst application liquid is less than 3.0, plating deposition is insufficient during the plating treatment, and a patterned metal layer is not formed. Further, when the pH of the catalyst application liquid exceeds 7.0, at the time of the plating treatment, the metal is also chromatographed on the substrate on which the patterned plating layer is not disposed, and the patterned metal layer having a specific shape is not formed. Further, when plating is deposited in a region other than the pattern-formed layer, the back surface of these metal layers is not considered to be black.

The catalyst-imparting liquid contains metal ions. The metal ion mentioned above can be mentioned as a kind of metal ion.

A solvent is usually contained in the catalyst-imparting liquid. As the solvent, water or an organic solvent is suitably used. As the organic solvent, a solvent which can penetrate into the patterned plated layer is preferable, and for example, acetone, ethyl acetate, ethyl acetate, ethylene glycol diacetate, cyclohexanone, and ethyl acetonide can be used. , acetophenone, 2-(1-cyclohexenyl)cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, Dimethyl carbonate, dimethyl cellosolve, and the like.

In addition, when water is used as the solvent, the water may be an aqueous solution of an acid or hydrazine, and examples of the acid contained in the acidic aqueous solution include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and the like; Sodium hydroxide, potassium hydroxide, magnesium hydroxide, etc. are mentioned.

The preparation method of the catalyst-imparting liquid is not particularly limited, and a specific metal salt is dissolved in a suitable solvent, and the pH is adjusted to a specific range using an acid or hydrazine as needed.

The concentration of the metal ions in the solution is not particularly limited, but is preferably 0.001 to 50% by mass, and more preferably 0.005 to 30% by mass.

Further, the contact time is preferably from about 30 seconds to about 24 hours, more preferably from about 1 minute to about 1 hour.

The amount of adsorption of the metal ions to be plated is different depending on the type of plating bath to be used, the type of catalyst metal, the type of interactive group of the pattern-coated layer, the method of use, and the like. The amount of adsorption is preferably 5 to 1000 mg/m ² , more preferably 10 to 800 mg/m ² , and particularly preferably 20 to 600 mg/m ² in terms of precipitation.

(Step 2-2: Plating treatment process)

Next, the pattern-coated layer to which the metal ions are applied is subjected to a plating treatment.

The method of the plating treatment is not particularly limited, and examples thereof include an electroless plating treatment or an electrolytic plating treatment (electroplating treatment). In this step, the electroless plating treatment may be separately performed, or the electrolytic plating treatment may be further performed after the electroless plating treatment is performed.

Further, in the present specification, a so-called silver mirror reaction is included as one of the above electroless plating treatments. Therefore, for example, by the silver mirror reaction or the like, the adhered metal ions are reduced, and a desired patterned metal layer can be formed, and thereafter, electrolytic plating treatment can be performed.

The process of the electroless plating treatment and the electrolytic plating treatment will be described in detail below.

The electroless plating treatment refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be precipitated at the time of plating are dissolved.

The electroless plating treatment in this step can be performed, for example, by washing a substrate having a patterned plated layer to which metal ions are applied, to remove excess metal ions, and then immersing in an electroless plating bath. As the electroless plating bath to be used, a known electroless plating bath can be used. Further, in the electroless plating bath, electroless plating after reduction and reduction of metal ions is performed.

The reduction of the metal ions in the patterned plated layer is different from the above-described method of using the electroless plating solution, and a catalyst activating solution (reducing solution) may be prepared as another step before the electroless plating treatment. The catalyst activating solution is a solution in which a reducing agent capable of reducing metal ions to a zero-valent metal is dissolved, and the concentration of the reducing agent is preferably 0.1 to 50% by mass, and more preferably 1 to 30% by mass based on the entire solution. As the reducing agent, a boron-based reducing agent such as sodium borohydride or dimethylamine borane, a reducing agent such as formaldehyde or hypophosphorous acid can be used.

At the time of impregnation, it is preferred to apply agitation or pulsation while immersing.

As a composition of a general electroless plating bath, in addition to a solvent (for example, water), it mainly contains 1. metal ions for plating, 2. a reducing agent, and an additive for improving the stability of metal ions (stabilizer). ). In addition to these components, the plating bath may contain a known additive such as a stabilizer of a plating bath.

The organic solvent to be used in the electroless plating bath is preferably a solvent which can be dissolved in water. From this viewpoint, it is preferable to use a ketone such as acetone or an alcohol such as methanol, ethanol or isopropyl alcohol. Copper, tin, lead, nickel, gold, silver, palladium, and rhodium are known as the type of metal used in the electroless plating bath. Among them, copper, silver, gold, and the like are preferable from the viewpoint of conductivity. Copper is preferred. Further, it is preferred to select an optimum reducing agent or additive based on the above metal.

The immersion time in the electroless plating bath is preferably from about 1 minute to 6 hours, more preferably from about 1 minute to 3 hours.

The electrolytic plating treatment refers to an operation of depositing a metal by a current using a solution in which metal ions to be precipitated at the time of plating are dissolved.

In addition, as described above, in this step, electrolytic plating treatment may be performed as needed after the electroless plating treatment. In this manner, the thickness of the formed pattern metal layer can be appropriately adjusted.

As a method of electrolytic plating, a conventionally known method can be used. Further, examples of the metal used for the electrolytic plating include copper, chromium, lead, nickel, gold, silver, tin, zinc, and the like. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable.

Further, the film thickness of the patterned metal layer obtained by electrolytic plating can be controlled by adjusting the metal concentration, current density, and the like contained in the plating bath.

The thickness of the patterned metal layer formed by the above process is not particularly limited, and an optimum thickness can be appropriately selected depending on the purpose of use. From the viewpoint of electrical conductivity, the thickness is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably It is 1 to 30 μm.

In addition, the type of the metal constituting the patterned metal layer is not particularly limited, and examples thereof include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable. More preferred are copper and silver.

The pattern shape of the pattern-shaped metal layer is not particularly limited, and since the pattern-like metal layer is disposed on the pattern-formed layer, in other words, the pattern-like metal layer is disposed along the shape of the pattern-coated layer, The pattern shape of the pattern-coated layer is adjusted, and for example, a mesh pattern or the like can be given. The patterned metal layer of the mesh pattern can be suitably used as the sensor electrode in the touch panel. When the pattern shape of the pattern metal layer is a mesh pattern, a range of one side length W of the lattice (opening) in the mesh pattern, a suitable form of the lattice shape, a line width of the pattern metal layer, and the above-described pattern shape The way to be coated is the same.

Further, the pattern-shaped plated layer after the above-described treatment contains metal particles produced by reduction of metal ions. The metal particles are dispersed in a pattern-like layer to be plated at a high density. Further, as described above, the interface between the patterned plated layer and the patterned metal layer is complicated in shape, and the patterned metal layer is further regarded as black due to the influence of such interface shape.

In the present invention, a coating layer may be provided on the formed patterned metal layer. In particular, in the case of a layer structure in which the surface of the patterned metal layer is directly visually observed, by making the surface of the patterned metal layer black (blackened), the metallic gloss effect of reducing the patterned metal layer can be obtained, and copper color can be obtained. Unobtrusive effect. In addition to this, anti-rust effect and anti-migration effect can also be obtained.

As a blackening method, there are a merging method and a replacement method. As a method of laminating, a method of laminating a coating layer (blackening layer) using a well-known method called blackening plating or the like can be used, and Nikka Black (Japan Chemical Industry Corporation) can be used. Manufactured, Ebony Chrome 85 series (manufactured by Metal Chemical Industry Co., Ltd.). Further, as a replacement method, a method of producing a coating layer (blackening layer) by vulcanizing or oxidizing the surface of the patterned metal layer, and replacing the surface of the patterned metal layer with a more expensive metal to produce a coating layer (blackening) Layer) method. As a method of vulcanization, Enplate MB 438A (manufactured by Meltex Co., Ltd.) or the like is used, and as the oxidation method, PROBOND 80 (manufactured by Rohm and Haas Electronic Materials Co., Ltd.) or the like can be used. As the plating substituted with a noble metal, palladium can be used.

<Laminated body>

The conductive laminate is formed by the above-described steps, and the conductive laminate includes a substrate having two main faces, a patterned plated layer disposed on at least one main surface of the substrate, and a patterned plated layer. A patterned metal layer (made of a metal component) containing a metal component. This conductive laminated body functions as a so-called transparent conductive laminated body, and can be suitably used for other uses (display screen use) other than touch panel use.

Further, the patterned plated layer contains an interactive group. As one embodiment, as described above, the composition for forming a layer to be plated is formed by applying energy in a pattern. Moreover, as one aspect of the pattern metal layer, it is formed by performing a plating process.

In the conductive laminate, the pattern-plated layer and the pattern-like metal layer may be disposed only on one main surface of the substrate, or the pattern-plated layer and the pattern may be disposed on both surfaces of the two main surfaces of the substrate. Metal layer. In the case where the pattern-coated layer and the pattern-like metal layer are disposed on both surfaces of the substrate, the above steps 1 and 2 may be performed on both surfaces of the substrate.

As described above, in the conductive laminate of the present invention, the metal component constituting the patterned metal layer is contained in the pattern-coated layer. For example, when the patterned metal layer is a copper plating layer (a metal layer made of copper), a copper component is contained in the pattern-formed layer.

Further, in the conductive laminate of the present invention, when the composition of the pattern-coated layer and the patterned metal layer is analyzed by energy dispersive X-ray analysis (EDS method), the pattern is formed. The ratio of the average peak intensity of the metal component source of the metal layer to the average peak intensity of the metal component source contained in the pattern-formed layer is 0.5 to 0.95 (preferably 0.65 to 0.95, more preferably 0.8 to 0.95).

More specifically, first, both the pattern-coated layer and the pattern-like metal layer are cut along the normal direction of the substrate of the conductive laminate, and the energy-dispersive X-ray analysis method is used for this. The section is analyzed for composition. A peak derived from a metal component constituting the patterned metal layer is observed from a region of the patterned metal layer. For example, in the case where the patterned metal layer is a copper layer, a peak derived from copper is observed. Further, as described above, the same metal component as the pattern metal layer is contained in the pattern-like plated layer. Therefore, the peak derived from the metal component contained can also be observed from the region of the patterned plated layer.

Next, the average peak intensity Pa of the source of the metal component constituting the patterned metal layer and the average peak intensity Pb of the source of the metal component contained in the patterned plated layer are respectively calculated, and the average peak intensity Pb is calculated with respect to the average peak. The ratio of the intensity Pa (Pb/Pa). When the obtained ratio (Pb/Pa) is within the above range, the amount of the metal component contained in the pattern-formed layer to be plated is a predetermined amount, and a desired effect can be obtained.

In addition, as a method of calculating the average peak intensity Pa, the composition analysis by the energy dispersion type X-ray analysis method is performed along the depth direction with respect to the cross section of the pattern metal layer obtained by the above method, and any 10 points or more is calculated. The peak intensities are taken as the average peak intensity Pa.

Further, regarding the calculation method of the average peak intensity Pb, the composition analysis by the energy dispersive X-ray analysis method is performed along the depth direction with respect to the cross section of the pattern-like plated layer obtained by the above method, and the calculation is performed arbitrarily. The peak intensities of 10 points or more are taken as the average peak intensity Pb.

The total light transmittance of JIS K7361-1 of the conductive laminated body is not particularly limited, and the total light transmittance is preferably 75% or more, and more preferably 80, from the viewpoint of better visibility when applied to a touch panel. %the above. The upper limit is not particularly limited, and is usually 98% or less.

It should be noted that the total light transmittance can be evaluated by using NDH7000 (manufactured by Nippon Denshi Kogyo Co., Ltd.).

The conductive laminate obtained by the above treatment preferably satisfies at least one of the following requirements X and Y.

Requirement X: Metal particles having an average particle diameter of 10 to 1000 nm exist in a surface layer region of 500 nm in the direction of the side of the pattern-coated layer from the interface between the pattern-coated layer and the pattern-like metal layer.

Requirement Y: The interface between the pattern-formed layer and the pattern-like metal layer has an uneven shape, and the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 to 1000 nm.

In addition, the definition of the above-described requirement X and the above-described requirement Y is the same as the requirement A and the requirement B described in the second embodiment to be described later, except for the type of the layer to be used, and the details thereof will be described below.

The obtained conductive laminate can be suitably used in a touch panel (preferably a capacitive touch panel). More specifically, it can be applied as a component constituting a touch sensor in a touch panel, and the patterned metal layer can be suitably applied to a sensor electrode that senses a change in electrostatic capacitance, and is used to apply a voltage to the sensor electrode. Lead wiring (peripheral wiring), etc.

When used in a touch panel, sometimes a cover layer or an OCA layer or the like is adjacently connected, and in these adjacent layers, undecanedioic acid, dodecanedioic acid, and tridecane may be added for the purpose of preventing copper rust. a phosphate compound such as a linear alkyl dicarboxylic acid such as a diacid, a monomethyl phosphate or a monoethyl phosphate; a pyridine compound such as quinaldine; a triazole, a carboxybenzotriazole, a benzotriazole or a naphthol; a triazole ring such as triazole, a tetrazole ring such as a 1H-tetrazole ring, a tetrazole ring system such as a benzotetrazole ring, or a 4,4'-butylene bis(6-tert-butyl-3-methylphenol). A bisphenol-based, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]-hindered phenolic system, a salicylic acid derivative system, an anthracene derivative A compound having a mercapto group such as an aromatic phosphate, a thiourea, a methylbenzotriazole or a 2-mercapto-oxazolthiol, a methylbenzothiazole or a mercaptothiazoline, or a triazine ring compound.

Further, a cyclic compound such as a crown ether or a cyclic phosphorus compound may be added to the adjacent layer.

Further, an anionic surfactant such as an alkylbenzenesulfonate, a linear alkylbenzenesulfonate, a naphthalenesulfonate or an alkenylsuccinate may be added to the adjacent layer, and PVP or the like may be used as the Lewis. Water-soluble polymer, arylsulfonic acid/salt polymer, polystyrenesulfonic acid, polyallylsulfonic acid, polymethallylsulfonic acid, polyvinylsulfonic acid, polyisoprenesulfonate Sulfonic acid group-containing polymerization of acid, -3-sulfopropyl acrylate homopolymer, -3-sulfopropyl methacrylate homopolymer, 2-hydroxy-3-propenylamine propane sulfonic acid homopolymer Things.

Further, a metal chelate compound such as a ruthenium pentoxide hydrate, an aluminum coupling agent, or a zirconium alkoxide, a zinc compound, an aluminum compound, a ruthenium compound, a ruthenium compound, and a calcium compound may be added to the adjacent layer. Examples of the zinc compound include zinc phosphate, zinc molybdate, zinc borate, and zinc oxide. Examples of the aluminum compound include aluminum dihydrogen triphosphate and aluminum phosphomolybdate. As the ruthenium compound, there are bismuth metaborate or the like. Examples of the ruthenium compound include cesium carbonate, ruthenium oxide, ruthenium acetate, bismuth metaborate, and metal ruthenium. As the calcium compound, there are calcium phosphate and calcium molybdate.

Further, an oxidizing agent such as ammonium persulfate, potassium persulfate or hydrogen peroxide may be added to the adjacent layer.

Further, dichloroisocyanurate and sodium metasilicate pentahydrate may be added in combination in the adjacent layer.

Further, a known copper corrosion inhibitor can also be used. Further, these compounds may be used in combination of two or more kinds.

As a modification of the first embodiment, an undercoat layer may be further included on the substrate. More specifically, as shown in FIG. 3, the undercoat layer 40 may be further disposed adjacent to the substrate 12 on the substrate 12. By providing an undercoat layer between the substrate and the patterned plated layer, the adhesion between the two is further improved.

The thickness of the undercoat layer is not particularly limited, but is usually preferably 0.01 to 100 μm, more preferably 0.05 to 20 μm, still more preferably 0.05 to 10 μm.

The material of the undercoat layer is not particularly limited, and a resin having good adhesion to the substrate is preferable. Specific examples of the resin may be, for example, a thermosetting resin, and may be a thermoplastic resin or a mixture thereof. Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, and a double resin. Maleic imine resin, polyolefin resin, isocyanate resin, and the like. Examples of the thermoplastic resin include a phenoxy resin, polyether oxime, polyfluorene, polyphenylene fluorene, polyphenylene sulfide, polyphenyl ether, polyether sulfimine, and ABS resin.

The thermoplastic resin and the thermosetting resin may be used singly or in combination of two or more. Further, a resin containing a cyano group can be used. Specifically, a "polymer containing a unit having a cyano group in a side chain" described in JP-A-2010-84196 [0039] to [0063] can be used.

Further, a rubber component such as NBR rubber (acrylonitrile, butadiene rubber) or SBR rubber (styrene-butadiene rubber) can also be used.

One of suitable methods for constituting the material of the undercoat layer is a polymer having a conjugated diene compound unit which can be hydrogenated. The conjugated diene compound unit means a repeating unit derived from a conjugated diene compound. The conjugated diene compound is not particularly limited as long as it has a molecular structure containing two carbon-carbon double bonds separated by one single bond.

One of suitable methods for the repeating unit derived from the conjugated diene compound is a repeating unit which is produced by a polymerization reaction of a compound having a butadiene skeleton.

The conjugated diene compound unit can be hydrogenated, and when the hydrogenated conjugated diene compound unit is contained, the adhesion of the patterned metal layer is further improved, which is preferable. That is, the double bond in the repeating unit derived from the conjugated diene compound can be hydrogenated.

In the polymer having a conjugated diene compound unit which can be hydrogenated, the above-mentioned interactive group may be contained.

Suitable examples of the polymer include nitrile rubber (NBR), carboxyl group-containing nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), and acrylonitrile-butadiene. a styrene copolymer (ABS resin) or a hydride thereof (for example, hydrogenated nitrile rubber) or the like.

Other additives (such as sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.) may be included in the undercoat layer.

The method for forming the undercoat layer is not particularly limited, and a method of laminating the resin to be used on the substrate, dissolving the resin to be used in a solvent capable of dissolving the necessary component, and performing the coating on the surface of the substrate by a method such as coating may be mentioned. Coating and drying methods.

In the coating method, the heating temperature and the time of the coating method may be selected so that the coating solvent can be sufficiently dried. From the viewpoint of the production suitability, it is preferred to select a heating condition in a range of a heating temperature of 200 ° C or less and a time of 60 minutes or less. Heating conditions in a range of a heating temperature of 40 to 100 ° C and a time of 20 minutes or less are selected. Further, the solvent to be used is appropriately selected depending on the resin to be used (for example, cyclohexanone or methyl ethyl ketone).

When the substrate on which the undercoat layer is disposed is used, the desired conductive laminate is obtained by performing the above steps 1 and 2 on the undercoat layer.

<<2th embodiment>>

The second embodiment of the conductive laminated body for a touch panel of the present invention includes the following conductive laminated body for a touch panel, and the conductive laminated body for the touch panel has a substrate and a pattern in the stated order. a resin layer and a patterned metal layer having two main faces, wherein the pattern-like resin layer is disposed on at least one main surface of the substrate, the patterned metal layer is disposed on the pattern-like resin layer, and the touch panel is electrically conductive The colloidal body satisfies at least one of the following requirements A and B.

Requirement A: Metal particles having an average particle diameter of 10 to 1000 nm exist in a surface layer region of 500 nm in the direction of the pattern-like resin layer from the interface between the patterned resin layer and the patterned metal layer.

Requirement B: The interface between the pattern-like resin layer and the patterned metal layer has an uneven shape, and the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 to 1000 nm.

When the conductive laminated body for a touch panel configured as described above is used, a desired effect can be obtained.

The substrate in the second embodiment of the conductive laminate for a touch panel is the same as the substrate described in the first embodiment, and the description thereof is omitted.

In the second embodiment of the conductive laminated body for a touch panel, the type of the resin constituting the patterned resin layer is not particularly limited, and a known resin can be used. For example, a thermosetting resin, a thermoplastic resin, or a thermoplastic resin can be used. For their mixture. Examples of the thermosetting resin and the thermoplastic resin include a thermosetting resin and a thermoplastic resin used in the undercoat layer of the first embodiment described above.

In addition, as a suitable aspect of the resin used for formation of the pattern-like resin layer, a resin formed by imparting energy to the compound having an interactive group and a polymerizable group, and a conjugated second which can be hydrogenated are mentioned. a polymer of an olefinic compound unit. The definition of a compound having an interactive group and a polymerizable group and a polymer having a conjugated diene compound unit which can be hydrogenated is as described above.

The type of the metal constituting the patterned metal layer is not particularly limited, and examples thereof include copper, chromium, lead, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and more preferably. Copper, silver.

The pattern shape of the pattern metal layer is not particularly limited, and examples thereof include a mesh pattern and the like. When the pattern shape of the pattern metal layer is a mesh pattern, a range of one side length W of the lattice (opening) in the mesh pattern, a suitable form of the lattice shape, a line width of the pattern metal layer, and the above-described pattern shape The way to be coated is the same.

The conductive laminated body for a touch panel of the present embodiment satisfies at least one of the following requirements A and B.

Requirement A: Metal particles having an average particle diameter of 10 to 1000 nm exist in a surface layer region of 500 nm in the direction of the pattern-like resin layer from the interface between the patterned resin layer and the patterned metal layer.

Requirement B: The interface between the pattern-like resin layer and the patterned metal layer has an uneven shape, and the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 to 1000 nm.

In the above-mentioned requirement A, the surface layer region in the direction of the pattern-like resin layer from the interface between the pattern-like resin layer and the pattern-like metal layer (in other words, the pattern-like resin from the surface on the pattern-like metal layer side of the pattern-like resin layer) The surface layer region in the layer side direction contains metal particles of a specific size, and light entering from the substrate side is absorbed by the surface plasmon resonance of the metal particles, and the patterned metal layer is regarded as blacker black.

The metal particles have an average particle diameter of 10 to 1000 nm, and are preferably 15 to 900 nm, and more preferably 20 to 800 nm, from the viewpoint that the patterned metal layer is considered to be blacker black.

Further, the average particle diameter is an average value of the primary particle diameters of the metal particles, and is a value obtained by measuring the diameters of arbitrary ten or more metal particles by an electron microscope and arithmetically averaging them. Further, when the metal particles are not in a perfect circular shape, the long diameter is taken as the diameter.

Further, when the metal particles are observed, the cross section of the conductive laminated body (the cross section perpendicular to the surface of the substrate in the conductive laminated body) is observed by an electron microscope (for example, SEM observation), and the self-patterned resin layer is observed. It is confirmed whether or not the surface layer of the pattern-like metal layer (the boundary line) has a surface layer of 500 nm in the direction of the pattern-like resin layer side.

In the surface layer region, when the thickness of the pattern-like resin layer exceeds 500 nm, the surface layer region refers to a region of at most 500 nm from the interface between the pattern-like resin layer and the patterned metal layer in the direction of the pattern-like resin layer side; When the thickness of the pattern-like resin layer is 500 nm or less, the surface layer region means the entire pattern-like resin layer.

In the above-described requirement B, when the interface between the pattern-like resin layer and the patterned metal layer has a specific uneven shape (concavo-convex surface), the reflection of light entering from the substrate side is suppressed by the uneven shape, and as a result, the patterned metal layer is Think blacker black.

The arithmetic mean roughness Ra of the unevenness of the interface between the patterned resin layer and the patterned metal layer is 5 to 1000 nm, and is preferably 10 to 900 nm, more preferably 10 to 900 nm, from the viewpoint that the patterned metal layer is considered to be blacker black. 15 to 800 nm.

As a method of measuring the arithmetic mean roughness Ra, the cross section of the conductive laminated body (the cross section perpendicular to the surface of the substrate in the conductive laminated body) can be observed by an electron microscope (for example, SEM observation) to obtain a pattern. The arithmetic mean roughness Ra of the interface (boundary line) between the resin layer and the patterned metal layer. More specifically, the arithmetic mean roughness Ra of the interface is defined as a value obtained by photographing the interface between the pattern-like resin layer and the patterned metal layer by an electron microscope, and then drawing the uneven shape of the interface in the photograph. The trace of the trace is regarded as the surface shape, and the value obtained by the calculation method of the arithmetic mean roughness (Ra) prescribed in JIS B 0601-2001 (ISO4287-1997) is defined as the arithmetic mean roughness Ra.

In addition, the average distance between the concave portions of the uneven shape is 10 to 1000 nm, and is preferably 15 to 900 nm, and more preferably 20 to 800 nm from the viewpoint that the patterned metal layer is considered to be blacker black.

The concave portion corresponds to a portion in which the metal in the patterned metal layer enters the inside of the patterned resin layer, in other words, it may be a convex portion that protrudes on the substrate side of the patterned metal layer.

The average distance between the concave portions is an average value of the distances between adjacent concave portions, and is a value obtained by measuring the distance between at least 10 or more adjacent concave portions and arithmetically averaging them. In addition, as a method of measuring the distance between the concave portions, similarly to the above-described arithmetic mean roughness Ra, a cross section perpendicular to the surface of the substrate in the conductive laminated body can be observed by an electron microscope (for example, SEM observation). A method of observing an interface (boundary line) between the patterned resin layer and the patterned metal layer.

The manufacturing method of the second embodiment of the conductive laminated body for a touch panel is not particularly limited as long as the above-described structure can be formed. For example, an interactive group is used in forming a patterned resin layer. In the case of a compound having a polymerizable group, the production methods of the first embodiment and the second embodiment described above can be carried out.

As another manufacturing method, for example, a method of roughening the surface of the patterned resin layer and then forming a patterned metal layer by a wet process such as sputtering or the above-described plating treatment may be mentioned.

The total light transmittance of the conductive laminate of the second embodiment is not particularly limited, and the suitable range is the same as the suitable range of the total light transmittance of the conductive laminate of the first embodiment.

Further, the undercoat layer may be further disposed adjacent to the substrate in the same manner as in the first embodiment.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto.

(Synthesis Example 1: Polymer 1)

Into a 2 L three-necked flask, 1 L of ethyl acetate and 159 g of 2-aminoethanol were placed, and the mixture was cooled in an ice bath. The internal temperature was adjusted to 20 ° C or lower, and 150 g of 2-bromoisobutyric acid bromide was added dropwise thereto. Thereafter, the internal temperature was raised to room temperature (25 ° C), and the reaction was carried out for 2 hours. After the reaction was terminated, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate phase was washed four times with 300 mL of distilled water, and then dried over magnesium sulfate to further distill off ethyl acetate to obtain 80 g of the material A.

Next, a raw material A 47.4 g, 22 g of pyridine, and 150 mL of ethyl acetate were placed in a 500 mL three-necked flask, and the mixture was cooled in an ice bath. The internal temperature was adjusted to 20 ° C or lower, and 25 g of acrylonitrile chloride was added dropwise thereto. Thereafter, it was raised to room temperature, and the reaction was carried out for 3 hours. After the reaction was terminated, 300 mL of distilled water was added to stop the reaction. Thereafter, the ethyl acetate phase was washed four times with 300 mL of distilled water, and then dried over magnesium sulfate to further distill off ethyl acetate. Thereafter, the following monomer M1 (20 g) was obtained by column chromatography.

[Chemical 6] Monomer M1

8 g of N,N-dimethylacetamide was placed in a 500 mL three-necked flask and heated to 65 ° C under a nitrogen stream. The monomer M: 1:14.3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.0 g, acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.5 g, and V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g were added dropwise thereto over a period of 4 hours. 8 g solution of N,N-dimethylacetamide.

After the completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, 41 g of N,N-dimethylacetamide was added, and the reaction solution was cooled to room temperature. To the reaction solution, 0.09 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 54.8 g of DBU (diazabicycloundecene) were added, and the reaction was carried out for 12 hours at room temperature. Thereafter, 54 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction liquid. After the reaction was terminated, reprecipitation was carried out with water, and the solid matter was taken out to obtain 12 g of a polymer 1.

The identification of the obtained polymer 1 was carried out using an IR measuring instrument (manufactured by Horiba, Ltd.). In the measurement, the polymer was dissolved in acetone using KBr crystals. According to the results of IR measurement, a peak was observed in the vicinity of 2240 cm-1, and it was found that acrylonitrile was introduced into the polymer as a nitrile unit. Further, it was found from the measurement of the acid value that acrylic acid was introduced as a carboxylic acid unit. This was dissolved in deuterated DMSO (dimethyl hydrazine) and measured by a 300 MHz NMR (AV-300) manufactured by Bruker. A broad peak corresponding to the nitrile-containing unit was observed at 2.5-0.7 ppm (5H) at 7.8-8.1 ppm (1H), 5.8-5.6 ppm (1H), 5.4-5.2 ppm (1H), 4.2-3.9 ppm ( 2H), 3.3-3.5 ppm (2H), 2.5-0.7 ppm (6H), a broad peak corresponding to a polymerizable group unit was observed, and a width corresponding to a carboxylic acid-containing unit was observed at 2.5-0.7 ppm (3H). Peak, it is known that the polymerizable group unit: nitrile group-containing unit: carboxylic acid group unit = 30:30:40 (mol%).

[Chemistry 7] Polymer 1

(Synthesis Example 2: Polymer 2)

20 g of N,N-dimethylacetamide was placed in a 500 ml three-necked flask and heated to 65 ° C under a nitrogen stream. The following monomer M2 was added dropwise thereto over a period of 4 hours: 20.7 g, 2-cyanoethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.5 g, and acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.4 g, V -65 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.0 g of a solution of N,N-dimethylacetamide 20 g. After the completion of the dropwise addition, the mixture was further stirred for 3 hours. Thereafter, 91 g of N,N-dimethylacetamide was added, and the reaction solution was cooled to room temperature.

0.17 g of 4-hydroxy TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) and 75.9 g of triethylamine were added to the reaction solution, and the mixture was reacted at room temperature for 4 hours. Thereafter, 112 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction liquid. After the reaction was terminated, reprecipitation was carried out with water, and the solid matter was taken out to obtain a polymer 2 (25 g).

[化8] Monomer M2

[Chemistry 9] Polymer 2

(Synthesis Example 3: Polymer 3)

In a 500 ml three-necked flask, 200 g of N,N-dimethylacetamide, 30 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, molecular weight: 25000), 2.4 g of tetraethylbenzylammonium chloride, and di-tert-amylhydroquinone were placed. 25 mg, Cyclomer A (manufactured by Daicel Chemical), 27 g, was reacted at 100 ° C for 5 hours under a nitrogen stream. Thereafter, the reaction liquid was reprecipitated, and the solid matter was collected by filtration to give polymer 3 (28 g).

[化10]

<Preparation of composition for forming a layer to be plated>

Add water, propylene glycol monomethyl ether, 2-propenylamine-2-methylpropane sulfonic acid, 6-acrylamide hexanoic acid, polymer 1-3, in a 200 ml beaker placed with a magnetic stirrer according to Table 1. Hexamethylene bis acrylamide, IRGACUREOXE02 (BASF), liquid was prepared to obtain compositions 1 to 6.

Further, in Table 1, the content of each component is expressed in terms of mass% with respect to the total amount of the composition.

[Table 1]

[11] 2-propenylamine-2-methylpropane sulfonic acid

[化12] 6-acrylamide caproic acid

[Chemistry 13] Hexamethylene bis acrylamide

<A composition for forming an undercoat layer>

100 g of hydrogenated nitrile rubber Zetpole 0020 (manufactured by Zeon, Japan) was dissolved in 900 g of cyclopentanone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the obtained solution was used as a composition for forming an undercoat layer.

<Examples 1 to 10 and Comparative Examples 1 to 3>

[Production of substrates S1-1 to S1-6 with a layer to be plated]

After glass substrate Gorilla glass (manufactured by Corning) was dried by heating at 150 ° C for 1 hour, hexamethyldiaziridine (manufactured by Tokyo Chemicals Co., Ltd.) and the composition for forming an undercoat layer were sequentially spin-coated at 1,500 rpm. After drying at 80 ° C for 5 minutes, a glass substrate with an undercoat layer was obtained. Next, the composition for forming a layer for plating (compositions 1 to 6) shown in Table 1 was spin-coated on the undercoat layer at 1,500 rpm for 1 minute, and dried at 80 ° C for 5 minutes. Thereafter, the substrate was subjected to UV irradiation (energy: 2 J, 10 mW; wavelength: 256 nm) with a negative mask having a line/space of 2 μm/98 μm in the atmosphere, using 1%. The sodium hydrogencarbonate is developed to form a patterned plated layer. The substrate with the plated layer obtained here was used as the substrates S1-1 to S1-6 with the plated layer.

[Production of substrate S1-7 with plated layer]

The plating was performed in the same process as the manufacturing process of the substrate S1-1 with the plated layer except that a mask having a pattern of 2 μm/98 μm was used without using a mask having a pattern of 2 μm/98 μm. The substrate S1-7 of the layer.

[Production of substrate S1-8 with plated layer]

The plating was performed in the same process as the manufacturing process of the substrate S1-1 with the plated layer except that a mask having a pattern of 2 μm/98 μm was used without using a mask having a pattern of 2 μm/98 μm. The substrate of the layer S1-8.

[Production of substrate S1-9 with plated layer]

The production process of the substrate S1-1 with the plated layer is carried out, except that the composition for forming an undercoat layer is not used, and the composition for forming a layer for plating is spin-coated after spin-coating hexamethyldioxane. The same process produces a substrate S1-9 with a plated layer.

[Production of substrate S1-10 with plated layer]

The glass substrate was replaced with PET (polyethylene terephthalate) substrate A4300 (manufactured by Toyobo Co., Ltd.), and the composition for forming an undercoat layer was directly spin-coated at 1,500 rpm for 1 minute without using hexamethyldioxane. Except for this, the substrate S1-10 having the plated layer was produced in the same manner as in the process of producing the substrate S1-1 with the plated layer.

The thickness of the patterned plated layer in the substrates S1-1 to S1-10 having the plated layer described above was 1.0 μm.

[Examples 1 to 10: Production of Conductive Laminates E1-1 to E1-10 having a patterned copper layer]

The surface of the substrates S1-1 to S1-10 having the plated layer which is not formed with the plated layer is covered with a protective tape (manufactured by Nitto Denko Corporation), and the Pd catalyst is supplied to the liquid MAT-2 at room temperature ( Only MAT-2A in Uemura Industrial Manufacturing Co., Ltd. was immersed in a 5-fold diluted solution for 5 minutes, and washed twice with pure water. Subsequently, it was immersed in a reducing agent MAB (manufactured by Uemura Industrial Co., Ltd.) at 36 ° C for 5 minutes, and washed twice with pure water. Thereafter, it was immersed in the activation treatment liquid MEL-3 (manufactured by Uemura Kogyo Co., Ltd.) for 5 minutes at room temperature, and was subjected to electroless plating solution Thru-cup PEA (Shangcun Industrial Co., Ltd.) at room temperature without washing. ) immersed for 60 minutes. The tape which was peeled off was washed twice with pure water, and the obtained substrate having the patterned plated layer and the patterned copper layer was used as the conductive layered bodies E1-1 to E1-10, respectively.

In addition, the above-mentioned "solution in which only MAT-2A in the Pd catalyst-providing liquid MAT-2 (manufactured by Uemura Industries Co., Ltd.) was diluted 5-fold" corresponds to a catalyst-imparting liquid containing palladium ions, and its pH was 3.5.

[Examples 11 to 12: Production of Conductive Laminates E1-11 to E1-12 having a patterned copper layer]

After dissolving 200 ml of 10% hydrochloric acid in palladium chloride (0.5 g), 700 ml of a 1 N aqueous sodium hydroxide solution was added. The catalyst-imparting liquid X and the catalyst-imparting liquid Y were prepared, and the catalyst-imparting liquid X was obtained by adjusting the pH of the Pd-catalyst-imparting liquid with 10% hydrochloric acid and a 1 N aqueous sodium hydroxide solution to adjust the pH to 4.4. It was obtained by adjusting its pH to 6.6.

In addition to the use of the catalyst-imparting liquid X, the use of the conductive layered body E1-1 was used, except that the solution of the Pd catalyst-imparting liquid MAT-2 (manufactured by Uemura Industrial Co., Ltd.) The same procedure was used to produce the conductive laminate E1-11.

In addition, the use of the catalyst-imparting liquid Y is carried out in addition to the use of the catalyst-imparting liquid Y, except that the solution of the Pd-catalyst-imparting liquid MAT-2 (manufactured by Uemura Kogyo Co., Ltd.) is used. The manufacturing method was the same to produce the conductive laminate E1-12.

[Comparative Example 1]

In the same procedure as described in paragraphs 0034 to 0037 of Patent Document 1, a pattern-like plating was obtained, except that the substrate with the undercoat layer was used without using the "base material of acrylic resin having a thickness of 2 mm and 100 mm square". A coated substrate S1-13 having a coating (corresponding to a resist).

Further, in Comparative Example 1, as described in Patent Document 1, a resist coating liquid containing colloidal palladium as a plating catalyst was used.

The surface of the substrate S1-13 having the plated layer on which the plated layer was not formed was covered with a protective tape (Nitto Denko), and then immersed in the activation treatment liquid MEL-3 (Shangcun Industrial) for 5 minutes at room temperature. The mixture was immersed in an electroless plating solution Thru-cup PEA (Shangcun Industrial) at room temperature for 60 minutes without washing. The tape which was peeled off was washed twice with pure water, and the obtained substrate having the patterned plated layer and the patterned copper layer was used as the conductive layered body E1-13.

[Comparative Example 2]

The surface of the patterned copper layer of the conductive laminated body E1-13 obtained in Comparative Example 1 was subjected to a blackening treatment using a blackening treatment liquid (manufactured by Carlit, Japan) to obtain a conductive laminated body E1-14.

[Comparative Example 3]

A 1 μm film of copper was formed on a glass substrate gorilla glass (manufactured by Corning) using a sputtering apparatus (manufactured by ULVAC). Thereafter, a patterned copper layer was formed by photolithography to obtain a conductive layered body E1-15 having a patterned copper layer.

[Comparative Examples 4 to 6]

After dissolving 200 ml of 10% hydrochloric acid into palladium chloride (0.5 g), 700 ml of a 1N aqueous sodium hydroxide solution was added. The catalyst-imparting liquid Z and the catalyst-imparting liquid W were prepared, and the catalyst-imparting liquid Z was obtained by adjusting the pH of the Pd-catalyst-imparting liquid with a 10% hydrochloric acid solution and a 1 N aqueous sodium hydroxide solution to adjust the pH to 1.8. It was obtained by adjusting its pH to 8.0.

The production of the conductive layered product E1-1 was carried out in addition to the use of the catalyst-imparting liquid Z, except that the solution of the Pd catalyst-imparting liquid MAT-2 (manufactured by Uemura Kogyo Co., Ltd.) was used. The same procedure was used to produce the conductive laminate E1-16. However, in the conductive laminated body E1-16, the metal was not precipitated, and the patterned metal layer was not formed.

MAT-2A using "Pd catalyst-imparting liquid MAT-2 (manufactured by Uemura Kogyo Co., Ltd.)" was used instead of the "solution of 5-time dilution of only MAT-2A in the MAT-2 (manufactured by Uemura Industries)". In addition, the conductive laminated body E1-17 was produced in the same manner as in the method of producing the conductive laminated body E1-1. In addition, the "MAT-2A of the Pd catalyst-providing liquid MAT-2 (manufactured by Uemura Kogyo Co., Ltd.)" is used in the case where it is not diluted, and the "Pd catalyst-imparting liquid MAT-2 (" The pH of MAT-2A" manufactured by Uemura Industrial Co., Ltd. was 2.9. However, in the conductive laminated body E1-17, the metal was not precipitated, and the patterned metal layer was not formed.

In addition, the use of the catalyst-imparting liquid W is carried out in addition to the use of the catalyst-imparting liquid W, except that the solution of the Pd-catalyst-imparting liquid MAT-2 (manufactured by Uemura Industrial Co., Ltd.) is used in a 5-fold dilution. The manufacturing method is the same process to produce the conductive laminate E1-18. Further, in the formed conductive laminated body E1-18, a metal layer is formed on substantially the entire surface of the substrate, and a specific patterned metal layer cannot be formed, which cannot be applied to a touch panel application. Therefore, various evaluations of the subsequent stage were not performed regarding the conductive laminated body E1-18.

<Energy dispersive X-ray spectrometry>

The patterned plated layer and the patterned metal layer of the conductive layered product E1-10 are cut along the normal direction of the substrate and in a direction orthogonal to the direction in which the pattern metal layer extends, and the scanning type is used. The microscope observes the cross section of the patterned plated layer and the patterned metal layer (see Fig. 4(A)). As shown in FIG. 4(A), a patterned metal layer (electroless copper plating), a patterned plating layer, and an undercoat layer were observed.

Next, using a transmission electron microscope, composition analysis was performed in the depth direction by energy dispersive X-ray analysis on the cross section of the patterned plated layer and the patterned metal layer. A map of peaks derived from copper is shown in Figure 4 (B). As shown in FIG. 4(B), in the region of the pattern-like metal layer, since the pattern-shaped metal layer is made of copper, a peak having a substantially constant intensity is calculated, and in the region where the pattern-like layer is plated, a pattern is observed. A peak derived from the same component contained in the plating layer. The average peak intensity Pa of the copper source constituting the patterned metal layer and the average peak intensity Pb of the copper component source contained in the pattern-formed layer were calculated by the above method, and the ratio (Pb/Pa) was determined. The results are shown in Table 2.

Further, Fig. 4(C) shows the results of observing the cross-sections of the patterned plated layer and the patterned metal layer by electron energy loss spectrum analysis (EELS method). The presence of carbon atoms was confirmed by the EELS method, and as shown in FIG. 4(C), the residual of carbon atoms was confirmed in the pattern-formed layer and the undercoat layer.

In the above, the method of using the conductive laminated body E1-10 is described in detail, and the same measurement is performed on the conductive laminated bodies E1-1 to E1-9 and the conductive laminated bodies E1-11 to E1-17. Ratio (Pb/Pa). Further, each of the examples and the comparative examples was evaluated in accordance with the following criteria. The results are summarized in Table 2.

"A": ratio (Pb/Pa) is 0.8 or more and 0.95 or less

"B": ratio (Pb/Pa) is 0.65 or more and less than 0.8

"C": ratio (Pb/Pa) is 0.5 or more and less than 0.65

"D": ratio (Pb/Pa) is less than 0.5

<evaluation>

(tone evaluation)

When the obtained conductive laminated body was visually observed from the substrate side, the color tone of the patterned metal layer (patterned copper layer) was evaluated in accordance with the following criteria. Further, "3" is preferable in practical use.

"1": is clearly regarded as copper (orange)

"2": considered to be slightly copper (orange)

"3": is considered black

Further, in the evaluation "3", in the case where the evaluation of the ratio (Pb/Pa) is "A", it is a dark black which is less luster.

(Electrical evaluation)

Conduction was performed in the same manner as in the above-described examples and comparative examples, except that the shape of the patterned metal layer formed was a mesh shape (the length of the metal portion was 2 μm and the length of the opening portion was 98 μm) using a specific photomask. Conductive laminates E3-1 to E3-17 for evaluation.

Using the obtained conductive laminates E3-1 to E3-17 for conductivity evaluation, the resistance value of the metal layer was measured by a low resistivity meter MCP-T610 (Mitsubishi Chemical Analysis Technology), and evaluated according to the following criteria. Practically preferred is "2".

“1”: resistance value is 1Ω/□ or more

"2": resistance value is less than 1 Ω / □

(section observation)

1 cm ² (1 cm × 1 cm) of the conductive laminate (E1-1 to E1-17) was fixed to an acrylic block, placed in a special mold, and an acrylic resin Acrylic One (Maruto) was injected. After the mold was placed in the mold, exposure was performed for 2 hours using an exposure apparatus ONE/LIGHT (Maruto Co., Ltd.) to cure the acrylic resin. After the curing, it was washed with acetone, and polished using a polishing machine ML-160A (Maruto Co., Ltd.) using a #400 polishing paper until the surface of the substrate was exposed, and then polished by Baikaloy 1.0 CR (BAIKOWSK INTERNATIONAL CORPORATION) until it became a mirror surface. Thereafter, the anti-charged gold was vapor-deposited on the surface, and then the cross section of the conductive laminate (the vertical surface with respect to the substrate surface) was observed by Hitachi High-Technologies S-3000, and the image analysis software was used. winRFFO" calculates the average particle diameter based on the shading of the image, and confirms whether or not the following requirement A or requirement B is satisfied. When any one of the following requirements A and B is satisfied, it is judged as "having" a fine structure, and when both the requirement A and the requirement B are not satisfied, it is judged as "none" fine structure.

Requirement A: There is an average particle in the surface region of 500 nm from the side of the plated layer (or the patterned plated layer) from the interface between the plated layer (or the patterned plated layer) and the patterned metal layer. Metal particles having a diameter of 10 to 1000 nm.

The requirement B: the interface between the plated layer (or the patterned plated layer) and the patterned metal layer has an uneven shape, and the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 ~1000nm.

In the following Table 2, "L/S (μm/μm)" means L (line) / S (space) of the patterned metal layer formed.

Further, in the column "method of forming a metal layer", "electroless" means that electroless plating treatment is performed, and "sputtering" means formation of a metal layer by sputtering.

Further, as described above, in Comparative Example 6, the metal layer was deposited on substantially the entire surface, and it was not applied to the touch panel application. From this point of view, various evaluations were not performed.

[Table 2]

In addition, the total light transmittance (JIS K7361-1) of the conductive laminates E1-1 to E1-17 measured by NDH7000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was 80% or more.

On the other hand, the total light transmittance (JIS K7361-1) of the conductive laminated body E1-18 is less than 80%.

As shown in the above Table 2, in the conductive laminate of the present invention, the patterned metal layer is considered to be blacker black, and is also excellent in conductivity.

On the other hand, in Comparative Examples 1 and 2 using the composition of Patent Document 1 and Comparative Example 3 in which the patterned metal layer was formed by the sputtering method, although the patterned metal layer was excellent in conductivity, the patterned metal was used. The color tone of the layer is copper, and the visibility is poor. In addition, as shown in the comparative example 2, the conductive layered product of Comparative Example 1 which was recognized as a copper color when the patterned metal layer was observed from the substrate side was observed from the substrate side after the blackening treatment. When the layer is layered, the hue does not turn black.

Further, as shown in Comparative Examples 4 to 6, when a catalyst-imparting liquid having a specific pH was not used, a conductive laminated body having a desired structure was not obtained, and a desired effect was not obtained.

<Example 13: Production of Conductive Laminate E2-1 for Touch Panel>

The same procedure as the method of manufacturing the conductive laminated body E1-1 is used, except that the mask is replaced with a single-sided single-layer type mask having a sensor portion and a peripheral wiring. A conductive laminated body having a patterned copper layer was prepared and used as a conductive laminated body E2-1 for a touch panel.

<Example 14: Production of Conductive Laminate E2-2 for Touch Panel>

In addition to replacing the mask with a double-sided type and having a touch panel fabrication mask for both the sensor portion and the peripheral wiring, and forming a patterned copper layer on both sides, the fabrication is performed in accordance with the conductive laminate E1-10. In the same manner, a conductive laminate having a patterned copper layer was prepared, and the surface of the copper was blackened by a blackening treatment liquid (manufactured by Carlit, Japan) to prepare a conductive laminated body E2-2 for a touch panel.

<Example 15: Production of Conductive Laminate E2-3 for Touch Panel>

A conductive laminated body E2-3 having a patterned copper layer was produced in the same manner as in the method of producing the conductive laminated body E1-1, except that the mask was replaced with a mask for producing a touch panel having only a peripheral wiring portion. '.

Next, ITO (indium tin oxide) film of 50 nm was formed on the surface of the conductive layered product E2-3' having the copper layer by using a sputtering apparatus. A photoresist TSMR-8900 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on the ITO layer to form a film of 2 μm. After prebaking at 90 ° C for 10 minutes, UV irradiation of 40 mJ was performed using a touch panel fabrication mask having a sensor portion. Thereafter, it was baked at 110 ° C for 10 minutes, after which the patterning of the photoresist was carried out using a 0.75% aqueous NaOH solution. Then, etching of the ITO layer was performed using an etching solution ITO-02 (manufactured by Kanto Chemical Co., Ltd.). Finally, the photoresist was completely removed by a 2% aqueous NaOH solution, and after washing, it was dried at 150 ° C for 30 minutes to prepare a conductive laminated body E2-3 for a touch panel.

The OCA (#8146-4: 100 μm thick) manufactured by 3M Co., Ltd. prepared above was attached to both surfaces of the conductive laminate obtained in the above Example 14. The outer shape of the obtained laminated body was roughly the same size as the slaked lime glass of 0.7 mm thick of the sensor size, and the FPC (flexible printed circuit board) was bonded by ACF (CP906AM-25AC) manufactured by Sony Chemical Co., Ltd. Then, the slaked lime glass was pasted on the top side, and the liquid crystal display was bonded to the bottom side to manufacture a touch panel.

In addition, the APC (CP906AM-25AC) manufactured by Sony Chemical Co., Ltd. was subjected to pressure bonding of FPC (Flexible Printed Substrate) on the conductive laminate obtained in the above Examples 13 and 15, and then bonded to a liquid crystal display panel to produce a touch. Control panel.

In Table 3, regarding "two-sided/one-sided", in the case where the sensor portion (sensor electrode) and the peripheral wiring are disposed only on one surface of the substrate, it means "single-sided" and is disposed on both sides of the substrate. The case of the sensor portion (sensor electrode) and the peripheral wiring means "two sides".

[table 3]

The composition of the touch panel obtained in Examples 13 to 15 is collectively shown in Table 3.

In the case where the conductive laminated bodies E2-1 to 2-3 for touch panels are used as the touch panel sensor, the pattern-like metal layer (sensor portion and/or peripheral wiring) formed by the above-described processing is It is considered to be black even when viewed from the substrate side, and can be used as a touch panel sensor.

100‧‧‧Electrically conductive laminated body for touch panel

12‧‧‧Substrate

22‧‧‧patterned metal layer

20‧‧‧patterned coating

30‧‧·coating film

40‧‧‧Undercoat

Fig. 1 is a cross-sectional view showing a first embodiment of a conductive laminated body for a touch panel of the present invention.

FIG. 2 is a cross-sectional view showing a manufacturing method of the first embodiment of the conductive laminated body for a touch panel of the present invention in the order of the process.

3 is a cross-sectional view showing a modification of the first embodiment of the conductive laminated body for a touch panel of the present invention.

Fig. 4 (A) is a scanning microscopic observation view of a cross section of the conductive laminate obtained in the example. Fig. 4(B) shows the results of composition analysis of copper in the cross section of the conductive laminate by the energy dispersive X-ray analysis method. Fig. 4(C) shows the results of carbon composition analysis of the cross section of the conductive laminate by the electron energy loss spectrum analysis method.

100‧‧‧Electrically conductive laminated body for touch panel

12‧‧‧Substrate

22‧‧‧patterned metal layer

20‧‧‧patterned coating

Claims (8)

A conductive laminated body for a touch panel, comprising: a substrate having two main surfaces; a patterned plated layer, wherein the patterned plated layer is disposed on at least one main surface of the substrate, and has a functional group that interacts with a metal ion; and a patterned metal layer disposed on the patterned plated layer; wherein the patterned plated layer includes a metal component constituting the patterned metal layer; In the energy dispersive X-ray analysis method, when the composition of the pattern-coated layer and the patterned metal layer is analyzed, the average peak intensity of the metal component constituting the pattern-shaped metal layer is The ratio of the average peak intensity of the above-mentioned metal component source contained in the plating layer is 0.5 to 0.95. The conductive laminated body for a touch panel according to claim 1, wherein the pattern-coated layer and the patterned metal layer are disposed on each of two main surfaces of the substrate. A conductive laminated body for a touch panel, comprising a substrate, a pattern-like resin layer, and a patterned metal layer, wherein the substrate has two main faces, and the patterned resin layer is disposed on at least one main surface of the substrate The patterned metal layer is disposed on the patterned resin layer; wherein the conductive laminate for the touch panel satisfies at least one of the following requirements A and B: A: from the patterned resin layer The interface of the patterned metal layer has metal particles having an average particle diameter of 10 to 1000 nm in a surface layer region of 500 nm in the direction of the pattern-like resin layer; and the material B: an interface between the pattern-like resin layer and the patterned metal layer The concave-convex shape is such that the arithmetic mean roughness Ra of the uneven shape is 5 to 1000 nm, and the average distance between the concave portions of the uneven shape is 10 to 1000 nm. The conductive laminate for a touch panel according to any one of claims 1 to 3, wherein the substrate is a glass substrate or a resin substrate. The conductive laminate for a touch panel according to any one of claims 1 to 3, wherein an undercoat layer is disposed adjacent to a main surface of the substrate. The conductive laminated body for a touch panel according to any one of claims 1 to 3, wherein the patterned metal layer contains copper. A touch panel comprising the conductive laminate for a touch panel according to any one of claims 1 to 6. A transparent conductive laminated body comprising: a substrate having two main faces; a patterned plated layer disposed on at least one main surface of the substrate and having a metal ion a functional group that interacts; and a patterned metal layer disposed on the patterned plated layer; wherein the patterned plated layer includes a metal component constituting the patterned metal layer; When the composition of the pattern-coated layer and the patterned metal layer is analyzed by the X-ray analysis method, the pattern is plated with respect to the average peak intensity of the metal component constituting the pattern-shaped metal layer. The ratio of the average peak intensity of the above-mentioned metal component source contained in the layer is from 0.50 to 0.95.